Physical Sciences and Mathematics Commons^™

Novel Electrochemical Detections Of Biologically And Environmentally Relevant Substances, Clarissa E. Tatum

Doctoral Dissertations

Development and studies of new electrochemical methods for the detection of various biologically and environmentally relevant substances are the focus of this dissertation. A dual amperometric sensor, capable of the simultaneous, real-time determination of NO and O,2, has been developed and optimized. Many tests were performed in order to reduce cross-talking between the two sensors, and an electro-deposited polymer, poly-5-amino-1-naphthol, was shown to reduce the cross-talking to insignificant levels. The use of bismuth-based electrodes in the detection of various metals has been explored. A bismuth bulk electrode has been developed, optimized, and used for the individual and simultaneous determination of …

Tantalum Carbene And Imide Complexes. Synthesis, Characterization, And Pathways Of Formation, Julia Kathryn Covington Abbott

Doctoral Dissertations

This dissertation focuses on two different types of organometallic compounds, carbenes and imides. The first project deals with the archetypal Schrock carbene, and the second project studies complexes that contain metal-nitrogen bonds, both amides and imides.

A summary of the research in this dissertation is discussed in Chapter 1. Chapter 2 begins the studies of the archetypal Schrock carbene (Bu^tCH₂)₃Ta=CHBu^t. The studies include the synthesis of deuterated compounds (Bu^tCD₂)₃TaCl₂ and Bu^tCD₂Li, observation and identification of the intermediate, Ta(CD₂Bu^{t …}

Spin-Lattice Coupling In The Iron-Pnictide High-Temperature Superconductors, Daniel E Parshall

Doctoral Dissertations

The recent discovery of the iron-pnictide superconductors has generated tremendous excitement, in part because there are many tantalizing similarities to the cuprate superconductors. As with the cuprates, it is strongly suspected that the spins contribute to superconductivity.

There seems to be a strong relationship between the lattice and magnetism in this system. Several authors have discussed the possibility of spin-phonon coupling, but direct experimental evidence has remained elusive.

This work discusses the relationship between the spins and the lattice in the $BaFe_{2}As_{2}$ family. We demonstrate the presence of negative thermal expansion in these materials, which is a strong indicator of …

A Visual Approach To Automated Text Mining And Knowledge Discovery, Andrey A. Puretskiy

Doctoral Dissertations

The focus of this dissertation has been on improving the non-negative tensor factorization technique of text mining. The improvements have been made in both pre-processing and post-processing stages, with the goal of making the non-negative tensor factorization algorithm accessible to the casual user. The improved implementation allows the user to construct and modify the contents of the tensor, experiment with relative term weights and trust measures, and experiment with the total number of algorithm output features. Non-negative tensor factorization output feature production is closely integrated with a visual post-processing tool, FutureLens, that allows the user to perform in depth analysis …

Human Decomposition Ecology At The University Of Tennessee Anthropology Research Facility, Franklin Edward Damann

Doctoral Dissertations

The University of Tennessee Anthropology Research Facility (ARF) is well known for its unique history as a site of human decomposition research in a natural environment. It has been integral to our understanding of the processes of human decomposition. Over the last 30 years 1,089 bodies have decomposed at this 1.28 acre facility, producing a density of 850 corpses per acre of land. This project evaluated the abiotic and biotic characteristics of the soil exposed to various levels of human decomposition in order to determine the effect on the physicochemical properties and the indigenous bacterial communities.

Specifically, 75 soil samples …

The Importance Of Chain Connectivity In The Formation Of Non-Covalent Interactions Between Polymers And Single-Walled Carbon Nanotubes And Its Impact On Dispersion, Dias Linton

Doctoral Dissertations

Polymer nanocomposites have garnered incredible promise in the field of material science due to the excellent mechanical strength, thermal and electrical conductivities of the nanoparticles and the extension of these properties to the processing flexibility inherent to plastics. However, practical realization of these nanoparticle-based materials has been hindered by the tendency of these nanoparticles to aggregate as a result of strong inter-particle forces. In this dissertation, we investigate the formation of non-covalent charge transfer interactions between polymers and single-walled carbon nanotubes (SWNTs) with the goal of optimizing interfacial adhesion and homogeneity of nanocomposites without modifying the SWNT native surface.

Nanocomposites …

Bioeconomic And Biophilic Intersect In Nature Centers - A Case Study Of One Nature Center, Carolyn Jeanne Price

Doctoral Dissertations

The purposes of this research were 1) to understand what stakeholders in one nature center are "thinking"about the focus of their center and the niche it occupies; 2) to characterize the role of one nature center in its local community; 3) to examine the nature center in terms of established characteristics of a "best" nature center; 4) to compare stakeholder perceptions with perceptions of directors of exemplar nature centers and environmental education organizations; and 5) to characterize visitor and member stakeholder perceptions and motivations in terms of the extrinsic value of ecosystem services, bioeconomics, versus the intrinsic value of nature, …

Differential Equation Models And Numerical Methods For Reverse Engineering Genetic Regulatory Networks, Mi Un Yoon

Doctoral Dissertations

This dissertation develops and analyzes differential equation-based mathematical models and efficient numerical methods and algorithms for genetic regulatory network identification. The primary objectives of the dissertation are to design, analyze, and test a general variational framework and numerical methods for seeking its approximate solutions for reverse engineering genetic regulatory networks from microarray datasets using the approach based on differential equation modeling. In the proposed variational framework, no structure assumption on the genetic network is presumed, instead, the network is solely determined by the microarray profile of the network components and is identified through a well chosen variational principle which minimizes …

Steps Toward Butternut (Juglans Cinerea L.) Restoration, Sunshine L. Brosi

Doctoral Dissertations

Butternut (Juglans cinerea L.), a lesser-known relative of black walnut (Juglans nigra L.), is a native tree species beneficial for wildlife, valuable for timber, and part of the great diversity of species in the eastern forests of North America. Populations of butternut are being devastated by butternut canker disease, caused by the fungus Sirococcus clavigignenti-juglandacearum (V.M.G. Nair, Kostichka, & Kuntz), which is thought to be introduced to North America. The disease causes multiple branch and stem cankers that eventually girdle trees. Small population sizes, lack of sprouting, and shade intolerance exacerbates the disease and results in permanent losses of butternut …

Polymeric Loop Formation At Hard And Soft Interfaces, Earl Ashcraft

Doctoral Dissertations

Copolymers are used to increase the interfacial strength of immiscible components and suppress recombination of the minor phase by steric hindrance. The experiments conducted in these studies are designed to investigate in situ polymer loop formation at soft interfaces and functionalized nanotube surfaces. Block copolymers are the most effective type of copolymer for compatibilization because they extend perpendicular to the interface, allowing good entanglement with the homopolymer chains. Multiblock copolymers are more effective than diblock copolymers for strengthening the interface because they can cross the interface multiple times, forming “loops” in each phase that provide entanglement points for the homopolymer. …

Sources And Transport Pathways Of Fecal Bacteria And Pathogens To Aquifers In Rural Bangladesh, Peter S. K. Knappett

Doctoral Dissertations

During the 1980’s millions of households in Bangladesh switched from drinking surface water to private groundwater wells to reduce their exposure to fecal microorganisms. Sadly, this switch to shallow groundwater resulted in the largest example of drinking water poisoning in history, with approximately 100 million people exposed to high concentrations of naturally occurring Arsenic in the groundwater. Spatial distribution of Arsenic in the shallow aquifers tends to be patchy, so the most economical mitigation option has been lateral switching from high Arsenic wells to nearby low Arsenic wells. The recently developed Arsenic flushing conceptual model, which explains the spatial distribution …

Density Functional Calculation Of X-Ray Absorption Spectra Within The Core Hole Approximation: An Implementation In Nwchem, William Ben Carlen

Doctoral Dissertations

Density functional theory is used to calculate the core excitation spectra of titanium structures. Specifically, the core-hole approximation is used. In this scenario, the excitation energies of core electrons are calculated using the approximation that the core energy level be frozen throughout the relaxation process of the orbitals. This allows a more acurate determination of the resulting X-ray spectra. The method described has been implemented in an NWChem module.

Supported Aqueous-Phase Catalysis For Atom Transfer Radical Polymerization, Ravi Aggarwal

Doctoral Dissertations

Atom transfer radical polymerization (ATRP) which utilizes transition metal based catalysts is a versatile methodology for the synthesis of a wide spectrum of polymers with controlled architectures. However, high concentrations of soluble catalyst required in an ATRP process makes the final polymer colored and toxic. Thus, the catalyst removal/reduction/recycling remains a challenge in the field of ATRP. Supported catalysts on insoluble solids such as silica gel, polystyrene beads, etc. have been used in ATRP to facilitate the catalyst recovery and recycling. However, the ability of the supported catalysts to mediate a polymerization is substantially reduced due to their reduced mobility …

Surface And Subsurface Structures Of The Western Valley And Ridge In Tennessee And Geometry And Kinematics That Permit Reconstruction Of The Tennessee Salient, Southern Appalachians, Jennifer Kathleen Whisner

Doctoral Dissertations

The southern and central Appalachian foreland fold-thrust belt comprises a series of orogen -scale curves that extend from Alabama to New York. One of these is the Tennessee salient, a foreland-convex curve that extends from Cartersville, Georgia, to Roanoke, Virginia. Development of a kinematic model for deformation in the salient has been hindered by a paucity of penetrative deformation in this generally low temperature, low volume-loss portion of the orogen.

Industry seismic reflection lines provide greater resolution of subsurface geometry of both the basement surface and the overlying fold-thrust belt, confirming some previous interpretations and changing others. A series of …

Multidimensional Liquid Chromatography Separations, Jacob N. Fairchild

Doctoral Dissertations

Many mixtures important to research consist of hundreds or even thousands of individual components of interest. These types of mixtures are far too complex to separate by a single chromatographic dimension in any reasonable amount of time. However, if a multidimensional approach is used, where a complex mixture is separated by an initial dimension, simpler fractions of that separation are collected and each of those fractions are analyzed individually, highly complex mixtures can be resolved in relatively short amounts of time. This dissertation serves as a guide to multidimensional chromatography, in particular, two-dimension liquid chromatography. There are many aspects of …

Spatiotemporal Dynamics In A Lower Montane Tropical Rainforest, Robert Michael Lawton

Doctoral Dissertations

Disturbance in a forest’s canopy, whether caused by treefall, limbfall, landslide, or fire determines not only the distribution of well-lit patches at any given time, but also the ways in which the forest changes over time. In this dissertation, I use a 25 year record of treefall gap formation find a novel and highly patterned process of forest disturbance and regeneration, providing a local mechanism by examining the factors that influence the likelihood of treefall. I then develop a stochastic cellular automaton for disturbance and regeneration based on the analysis of this long term data set and illustrate the potential …

Interplay Between Structure And Chemistry Of Materials And Their Physical Properties, Alaska Subedi

Doctoral Dissertations

First principles calculations provide a powerful tool for sorting out the interplay of chemical composition and structure with the physical properties of materials. In this dissertation, I discuss the physical properties and their microscopic basis within this framework for following illustrative examples. (i) The Zintl phase hydrides, where I find H is anionic and the formation of covalent sp2 bonds in the Al/Ga/Al-Si planes, which is a highly unusual bonding configuration for these elements. (ii) PbTe, which shows strong coupling between the longitudinal acoustic and transverse optic modes that may explain its low thermal conductivity. (iii) The double perovskites BiPbZnNbO6 …

Effects Of 2000-2050 Global Climate Change On Ozone And Particulate Matter Air Quality In The United States Using Models-3/Cmaq System, Yun-Fat Lam

Doctoral Dissertations

The Models-3/Community Multi-scale Air Quality modeling system (CMAQ), coupled with Goddard Institute for Space Studies (GISS) atmospheric General Circulation Model (GCM), fifth Generation Mesoscale Model system (MM5), and Goddard Earth Observing System-CHEMistry (GEOS-Chem), was used to simulate atmospheric concentration of ozone and particulate matter over the continental United States 12-km and 36-km (CONUS) domains at year 2000 and year 2050. In the study, GISS GCM model outputs interfaced with MM5 were utilized to supply the current and future meteorological conditions for CMAQ. The conventional CMAQ profile initial and boundary conditions were replaced by time-varied and layer-varied GEOS-Chem outputs. The future …

Towards Simulations Of Binary Neutron Star Mergers And Core-Collapse Supernovae With Genasis, Reuben Donald Budiardja

Doctoral Dissertations

This dissertation describes the current version of GenASiS and reports recent progress in its development. GenASiS is a new computational astrophysics code built for large-scale and multi-dimensional computer simulations of astrophysical phenomena, with primary emphasis on the simulations of neutron star mergers and core-collapse supernovae. Neutron star mergers are of high interest to the astrophysics community because they should be the prodigious source of gravitation waves and the most promising candidates for gravitational wave detection. Neutron star mergers are also thought to be associated with the production of short-duration, hard-spectral gamma-ray bursts, though the mechanism is not well understood. In …

The Maximum Clique Problem: Algorithms, Applications, And Implementations, John David Eblen

Doctoral Dissertations

Computationally hard problems are routinely encountered during the course of solving practical problems. This is commonly dealt with by settling for less than optimal solutions, through the use of heuristics or approximation algorithms. This dissertation examines the alternate possibility of solving such problems exactly, through a detailed study of one particular problem, the maximum clique problem. It discusses algorithms, implementations, and the application of maximum clique results to real-world problems. First, the theoretical roots of the algorithmic method employed are discussed. Then a practical approach is described, which separates out important algorithmic decisions so that the algorithm can be easily …

New Electrochemical And Optical Detection Methods For Biological And Environmental Applications, Royce Nicholas Dansby-Sparks

Doctoral Dissertations

Detection of chromium and vanadium is of interest for biomedical and environmental applications. The two metals have narrow limits between being essential and toxic for humans. Ultra-sensitive techniques have been studied to measure Cr and V at low concentrations found in human blood and environmental samples. Bismuth film and mercury-alloy electrodes have been developed as alternatives to traditional Hg-based electrodes for Cr and V detection. While catalytic adsorptive stripping voltammetry (CAdSV) has been used to detect Cr and V, little is known about the process. The mechanisms of CAdSV have been probed to provide a better understanding of its exceptional …

Mixture Of Factor Analyzers With Information Criteria And The Genetic Algorithm, Esra Turan

Doctoral Dissertations

In this dissertation, we have developed and combined several statistical techniques in Bayesian factor analysis (BAYFA) and mixture of factor analyzers (MFA) to overcome the shortcoming of these existing methods. Information Criteria are brought into the context of the BAYFA model as a decision rule for choosing the number of factors m along with the Press and Shigemasu method, Gibbs Sampling and Iterated Conditional Modes deterministic optimization. Because of sensitivity of BAYFA on the prior information of the factor pattern structure, the prior factor pattern structure is learned directly from the given sample observations data adaptively using Sparse Root algorithm. …

Boron And Titanium(Iv) Halide Mediated Reactions, Michael Patrick Quinn

Doctoral Dissertations

This dissertation summarizes research efforts focused on the use of boron and transition metal halides to form new carbon-carbon and carbon-halide bonds. The boron halide mediated alkyne-aldehyde coupling reaction to generate 1,3,5-triaryl-1,5-dihalo-1,4-dienes was reinvestigated in an attempt to explain the stereochemistry observed during changing of both the mode of addition and the reaction temperature. Either (Z,Z)-1,4-dienes or (Z,E)-1,4-dienes can be the predominant product depending on reaction conditions used. This mechanistic investigation also led to the discovery of several novel reactions. These include the stereoselective preparation of (Z)-3-chloroallylic ethers from the reaction of alkenylboron dichlorides with aryl aldehydes in the presence …

Ads/Cft Correspondence And Hydrodynamics Of Relativistic Heavy Ion Collisions, James Ethan Alsup

Doctoral Dissertations

The experiments performed at the Relativistic Heavy Ion Collider (RHIC) at Brookhaven National Lab have discovered a state of matter called the strongly coupled quark-gluon plasma (sQGP). The strong coupling has limited the ability of the standard theory to describe such matter, namely Quantum Chromodynamics (QCD). However, string theory's anti-de Sitter/conformal field theory (AdS/CFT) correspondence has provided a new way to study the situation and in an analytical manner. So far, hydrodynamic properties of RHIC's plasma, such as elliptic flow and longitudinal expansion, have been seen to follow from classical supergravity calculations. In this dissertation I discuss some of the …

Hairy Particles: Polymer Brush-Supported Organocatalysts And Asymmetric Mixed Homopolymer Brushes, Xiaoming Jiang

Doctoral Dissertations

This dissertation presents the synthesis and studies of polymer brush-supported organocatalysts and asymmetric mixed homopolymer brushes grafted on particles. The brushes were synthesized from initiator-functionalized particles by surface-initiated “living” radical polymerizations.

Polymer brush-supported organocatalysts were designed to combine the advantages of both soluble polymer- (high activity) and crosslinked insoluble polymer-supported catalysts (recyclability). Chapter 1 describes the synthesis of a polymer brush-supported 4-N,N-dialkylaminopyridine (DAAP) catalyst from initiator-functionalized latex particles by surface-initiated nitroxide-mediated radical polymerization (NMRP). The hairy particles efficiently catalyzed the acylation of secondary alcohols and Baylis-Hillman reaction and were recycled  six times with no or negligible decrease in the …

Optimal Control Of Species Augmentation Conservation Strategies, Erin Nicole Bodine

Doctoral Dissertations

Species augmentation is a method of reducing species loss via augmenting declining or threatened populations with individuals from captive-bred or stable, wild populations. In this dissertation, species augmentation is analyzed in an optimal control setting to determine the optimal augmentation strategies given various constraints and settings. In each setting, we consider the effects on both the target/endangered population and a reserve population from which the individuals translocated in the augmentation are harvested. Four different optimal control formulations are explored. The first two optimal control formulations model the underlying population dynamics with a system of ordinary differential equations. Each of these …

On Conjectures Concerning Nonassociate Factorizations, Jason A Laska

Doctoral Dissertations

We consider and solve some open conjectures on the asymptotic behavior of the number of different numbers of the nonassociate factorizations of prescribed minimal length for specific finite factorization domains. The asymptotic behavior will be classified for Cohen-Kaplansky domains in Chapter 1 and for domains of the form R=K+XF[X] for finite fields K and F in Chapter 2. A corollary of the main result in Chapter 3 will determine the asymptotic behavior for Krull domains with finite divisor class group.

Elasticity Of Krull Domains With Infinite Divisor Class Group, Benjamin Ryan Lynch

Doctoral Dissertations

The elasticity of a Krull domain R is equivalent to the elasticity of the block monoid B(G,S), where G is the divisor class group of R and S is the set of elements of G containing a height-one prime ideal of R. Therefore the elasticity of R can by studied using the divisor class group. In this dissertation, we will study infinite divisor class groups to determine the elasticity of the associated Krull domain. The results will focus on the divisor class groups Z, Z(p infinity), Q, and general infinite groups. For the groups Z and Z(p infinity), it has …

A Method To Accomplish The Optimal Control Of Continuous Dynamical Systems With Impulse Controls Via Discrete Optimal Control And Utilizing Optimal Control Theory To Explore The Emergence Of Synchrony., Rachel Natalie Graves

Doctoral Dissertations

This research concerns the development of new optimal control methodologies and applications. In the first chapter we consider systems of ordinary differential equations subject to a restricted number of impulse controls. Examples of such systems include tumor growth, in which case the impulsive control is the administration of medication, and ecological invasion, in which case the impulse control is the release of predator species. Impulse control problems are typically solved via related partial differential equations known as quasi-variational inequalities. We show that these types of impulse control problems can be formulated as a discrete optimal control problems. Furthermore, this formulation …

Development Of Nanomechanical Sensors For Environmental Contaminate Screening Using Protein Functionalized Microcantilevers, Kasey L. Hill

Doctoral Dissertations

The development of real time, label-free biosensors based on ligand-induced nanomechanical responses of microcantilevers (MCs) allows for sensitive and selective detection. High sensitivity is afforded by the MCs small dimensions. Immobilizing biomolecular recognition phases imparts selectivity from bioaffinity interactions. Biological sensors on a MC platform utilize various proteins, such as antibodies and nuclear receptors, which can be used to detect and screen for potential environmental contaminants.

The interaction between contaminants and immobilized receptors induces an apparent surface stress that leads to static bending of the MC, which is monitored by an optical beam bending technique. Biofunctionalized MCs can provide high …